JPH0610756B2 - Silver halide color-reversal photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color reversal photographic material which is excellent in image sharpness and sensitivity and has little gradation change accompanying sensitized development.

(Prior Art) A silver halide color photographic material for photographing is required to have high image quality, high sensitivity and processing stability regardless of whether it is negative or reversal. Sharpness, graininess, color reproduction, etc. are important for image quality, and good gradation balance is important for processing stability in both standard processing and sensitization processing of color reversal photographic materials.

It is generally known that in a multilayer color photographic material having a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, light scattering by silver halide grains tends to reduce the sharpness of the emulsion layer located below. .

U.S. Pat. No. 4,439,520 describes a color photographic light-sensitive material in which sharpness, sensitivity and graininess are improved by using tabular silver halide emulsion grains. However, such a tabular silver halide emulsion causes a great problem in the reversal processing of a negative type emulsion.
That is, in the color reversal processing, a negative reversal image is obtained by black-and-white development (first development) of the negative type silver halide, and then fogging the residual silver halide to develop the color. This black-and-white developing solution contains a silver halide solvent such as potassium thiocyanate and sodium sulfite, and while the development accelerating effect can be obtained by dissolution physical development, in the case of using particles having photosensitivity mainly on the particle surface, This results in a loss of sensitivity due to surface dissolution of the particles. In addition, the dissolution of the unsensitized particles causes a change in the apparent sensitivity of the reversal color image, which greatly changes the gradation particularly during sensitized development.

In recent years, in color photographic materials for high-sensitivity photography, even in reversal light-sensitive materials, a silver halide emulsion layer having blue, green, and red color sensitivity is usually composed of a plurality of emulsion layers having different sensitivities. . At this time, it was found that the silver halide dissolving action of the black-and-white developing solution had an interaction in the shapes of the emulsions used in the high, medium and low sensitive layers. That is, by using tabular grains in the high-sensitivity and / or medium-sensitivity layer, a silver halide color reversal photographic material with improved sharpness can be obtained, but the high dissolution physical activity of tabular grains is Dissolution is excessively promoted, which brings about the adverse effects such as the loss of sensitivity of the final color reversal image, the gradation variation, and the gradation balance change as described above. These drawbacks are emphasized by the small size of the emulsion close to the tabular grains, and a radical solution is desired. In particular, in the case of color reversal photographic materials, since the final quality is determined by the delicate color balance, the above defects have a serious influence on the quality.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide color reversal photographic material having excellent sharpness and graininess and high sensitivity.

It is a second object of the present invention to provide a silver halide color reversal photographic material which gives a color reversal image with stable gradation and gradation balance by reversing the negative silver halide emulsion layer group.

A third object of the present invention is to provide a silver halide color reversal photographic material which gives good gradation by sensitized development.

A fourth object of the present invention is to provide a method for providing a color reversal image having excellent sharpness and graininess, high sensitivity, and high processing stability.

(Means for Solving the Problems) The above objects of the present invention are such that at least 50% of the total projected area of silver halide grains contained in one silver halide emulsion layer coated on a support is A silver halide emulsion layer occupied by tabular silver halide grains having an average aspect ratio of 5 or more and having substantially the same color sensitivity as this silver halide emulsion layer but having a low photosensitivity It has been achieved by a silver halide color reversal photographic material which undergoes black and white development followed by color processing, characterized in that it contains chemically sensitized silver halide grains inside.

The present invention will be described in detail below.

The tabular silver halide emulsion and the internally chemically sensitized silver halide emulsion of the present invention are preferably both negative type.

In the present invention, the tabular silver halide grains have a diameter of 5.0.
It is less than or equal to μ, preferably 0.5 to 3.0 μ. The thickness is 0.4 μ or less, preferably 0.3 μ or less 0.0
It is 5 μ or more, more preferably 0.2 μ or less and 0.05 μ or more.

The aspect ratio of the tabular grains is 5 or more, preferably 5 to 30, and more preferably 5 to 8.

In general, tabular silver halide grains are tabular having two parallel planes, so that the "thickness" in the present invention is represented by the distance between two parallel planes constituting the tabular silver halide grain. .

The proportion of tabular silver halide grains in the emulsion containing tabular silver halide grains used in the present invention is preferably 50% or more, and preferably 70% or more, with respect to the total projected area. Is more preferable, and 90% or more is particularly preferable.

These tabular silver halide grains are disclosed in Japanese Examined Patent Publication No. 47-11, 38.
As described in No. 6 and the like, it is also possible to use the silver halide grains in a dispersible state of particle size and / or thickness in a monodisperse state.

Here, the tabular silver halide grains being monodisperse means that 95% of the grains are within ± 60% of the number average grain size,
It is preferably a dispersion system having a size within ± 40%. Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains.

The halogen composition of the tabular grains is preferably silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride or silver iodochloride. Silver iodobromide, silver bromide, silver chlorobromoiodide or a mixture thereof is particularly preferred for use in the high-sensitivity light-sensitive material.
In the case of silver iodobromide, the silver iodide content is usually 40 mol% or less, preferably 20 mol% or less, more preferably 1 mol% or less.
It is 0 mol% or less.

The tabular grains may be composed of a uniform halogen composition or may be composed of two or more phases having different halogen compositions.

For example, when silver iodobromide is used, the tabular silver iodobromide grains having a layered structure composed of a plurality of phases each having a different iodide content can be used. JP-A-58-
113,927, JP-A-58-113,928, JP-A-59-99,433, JP-A-59-119,34.
No. 4, JP-A-59-119350, and the like, preferred examples of the halogen composition of tabular silver halide grains and the distribution of halogen in the grains are described.

The tabular grains can be selected from those formed from (111) planes, (100) planes, or a mixture of (111) planes and (100) planes.

Regarding the formation size of the latent image, the particles may be such that the latent image is mainly formed on the surface of the particle, or the latent image may be mainly formed inside the particle. Further, the particles may be such that a latent image is formed on the surface of the particle and inside the particle.
Particles in which a latent image is formed inside the particles are preferably used in the present invention.

Next, a method for producing tabular silver halide grains will be described.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

For example, a seed crystal in which tabular grains are present at 40% or more by weight is formed in an atmosphere of a relatively low pBr value of pBr 1.3 or less, and a seed crystal is added while maintaining the same pBr value and simultaneously adding a silver and halogen solution. Obtained by growing crystals.

During this grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the amount of the solvent, the addition rate of the silver salt used during grain growth, and the halide.

The grain shape (diameter / thickness ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent, if necessary, during the production of the tabular silver halide grains of the present invention. The amount of the solvent used is preferably 10 ^{−3 to} 1.0% by weight of the reaction solution, and particularly preferably 10 ⁻² to 10 ⁻¹ % by weight.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be increased. On the other hand, there is also a tendency that the particle thickness increases with the amount of solvent used.

Examples of the silver halide solvent often used include ammonia, thioethers and thioureas.

These silver halide solvents are added during the production of the tabular silver halide grains of the present invention to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the silver salt solution (eg, AgNO ₃ aqueous solution) and the halide solution (eg, KBr aqueous solution) is preferably used.

The tabular silver halide grains used in the present invention and the silver halide emulsion containing them are more specifically described in US Pat. Nos. 4,434,226, 4,439,520 and 4,414,310, 4,425,425, 4,399,215, 4,435,501, 4,386,156, 4,400,463, 4, 414, 306, 4,425, 426, European Patent 84,637A
2, JP-A-59-99433, Research Disclosure No. 22534 (January 1983) and the like.

The thickness of the layer containing tabular silver halide grains is 0.3-
It is preferably 6.0 μ, and particularly preferably 0.5 to 4.0 μ.

The coating amount of tabular silver halide grains is 0.1 to 6 g /
It is preferably m ² , particularly 0.3 to 3 g / m ² .

"Having substantially the same photosensitivity" means that, as seen in a normal multilayer silver halide color photographic material, it is blue-sensitive,
It means the same color sensitivity in a green-sensitive or red-sensitive emulsion layer, and means that the emulsion layer has photosensitivity in common in the main region of the visible spectrum. Usually, a two-layer or three-layer emulsion having the same color sensitivity but different sensitivities is used.

Next, a description will be given of a silver halide grain in which the inside of the grain is chemically sensitized.

The silver halide grain chemically sensitized in the grain used in the present invention is composed of a core portion and a shell portion, and has a sphere-converted diameter of 5.0 μm or less in which the surface of at least the core is chemically sensitized. Is a particle of 3 μm or less.

The molar ratio of Ag ⁺ ions forming the core and the shell is 1:
19-99: 1, preferably 1: 1 to 19:
It is 1.

The halogen composition of the core and shell is usually silver bromide, silver iodobromide,
It is silver chlorobromide, silver chloroiodobromide, silver chloride or silver iodochloride, with silver iodobromide being preferred. The silver iodide content is usually 40 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less.
It is not more than mol%. The halogen composition of the core and the shell may be the same or different.

The silver halide grains chemically sensitized inside may be tabular grains having an aspect ratio of 5 or more as disclosed in the present invention, ordinary silver halide grains or a mixture thereof.
Here, as an ordinary silver halide grain, for example, a regular grain having a regular crystal such as a cube, an octahedron, a tetradecahedron, a rhodohedron or an irregular crystal such as a spherical or potato-shaped grain. Mention may be made of polydisperse and monodisperse particles having a shape.

Preferably, flat plate, octahedron, cubic, spherical or 1
Internal latent image forming emulsions of tetrahedral grains can be used in the present invention.

The crystal habit and shape of the core and shell may be the same or different.

The shell surface need not be chemically sensitized, but
If necessary, it is possible to carry out chemical sensitization.

For silver halide grains chemically sensitized inside the grains, after the core grains are chemically sensitized, (1) silver ions and halogen ions are added to precipitate, or (2) the size is obviously smaller than the core grains. It can be produced by a method of adding fine particles and aging in Oswald. More specifically, including the manufacturing method, for example, US Pat. Nos. 3,206,313 and 33173.
22, No. 3,917,485, No. 3,979,213 and the like.

In the photographic emulsion layers other than the tabular or grain-sensitized silver halide emulsion layers chemically sensitized in the present invention, silver bromide, silver iodobromide,
Any silver halide of silver chlorobromide, silver chloroiodobromide, silver chloride, and silver chloroiodide may be used, and silver iodobromide is preferred for the high-sensitivity light-sensitive material. In the case of silver iodobromide, the silver iodide content is usually 40 mol% or less, preferably 20 mol% or less,
More preferably, it is 10 mol% or less.

The above-mentioned silver halide grains may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as spheres, twin crystals. It may have a crystal defect such as a plane or a composite form thereof. Also, a mixture of particles having various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 micron or less or large grains with a projected area diameter of up to about 10 microns, or a monodisperse emulsion having a narrow distribution.
Alternatively, a polydisperse emulsion having a wide distribution may be used.

Further, tabular grains having an aspect ratio of 5 or more may be used in the above emulsion layer.

The crystal structure of the above emulsion grains may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains were obtained from British Patent No. 1,027,146, U.S. Patent Nos. 3,505,068 and 4,444,877.
And Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Pat.
684, 4,142,900, 4,459,353, British patent 2,0
38,792, U.S. Pat.Nos. 4,349,622, 4,395,478, and
4,433,501, 4,463,087, 3,656,962, 3,85
2,067, JP-A-59-162540 and the like.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image in both the surface and the inside.

The silver halide photographic emulsion that can be used in the present invention can be produced by appropriately using known methods. For example, Research Disclosure, 176, No. 17643 (December 1978).
Mon.) 22-23, "I. Emulsion Prepar
and Types) ”and ibid., 187, No. 1871
6 (November 1979), p.648. The photographic emulsion that can be used in the present invention is described in "Graphics and Chemistry" by Graphide, published by Paul Montell (P.
Glafkides, Chimie et Physique Photographique Paul M
ontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion
Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (V.
L. Zelikman et al, Making and Coating Photographic E
mulsion, Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

If necessary, various silver halide solvents (for example, ammonia, Rhodan potassium or U.S. Pat. No. 3,271,157, JP-A-51-123) can be used to adjust the photographic emulsion that can be used in the present invention.
60, JP-A-53-82408, JP-A-53-14
It is also possible to use thioethers and thione compounds described in JP-A No. 4319, JP-A No. 54-100717 or JP-A No. 54-155828.

The silver halide emulsion consisting of regular grains that can be used in the present invention can be obtained by controlling pAg and pH during grain formation. For more information, see, for example, Photographic Science and Engineering.
e and Engineering) Volume 6, 159-165 (1962);
Journal of Photographic Science (Jou
rnal of Photographic Science), Volume 12, 242-2
51 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

The monodisperse emulsion comprises silver halide grains having an average grain diameter of greater than about 0.1 micron, at least 9
Emulsions such that 5% by weight are within ± 40% of the average grain diameter are typical. The average grain diameter is 0.25 to 2 microns and at least 95% by weight or (number of grains) at least 95% of the silver halide grains have an average grain diameter of ± 2.
Emulsions such as within 0% can be used in the present invention.
A method for producing such an emulsion is described in U.S. Pat.No. 3,574,628,
No. 3,655,394 and British Patent No. 1,413,748. Further, JP-A-48-8600 and 51-39.
027, 51-83097, 53-13713.
No. 3, No. 54-48521, No. 54-99419,
Monodisperse emulsions such as those described in JP-A-58-37635 and JP-A-58-49938 can also be preferably used in the present invention.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

In order to remove the soluble silver salt from the emulsion before and after physical ripening, a Nudel water washing, a flocculation sedimentation method, an ultrafiltration method or the like is used.

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are those described in Research Disclosure No. 17643 (December 1978) and N.
No. 18716 (November 1979),
The relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention, specific examples of which are mentioned above in Research Disclosure.
No. 17643, VII-C to G. As the dye-forming coupler, a coupler which gives the three primary colors of the subtractive method (that is, yellow magenta and cyan) by color development is important, and specific examples of the diffusion-resistant hydrophobic 4-equivalent or 2-equivalent coupler are described above. In addition to the couplers described in the patents described in Research Disclosure No. 17643, VII-C and D, the following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and US Pat.Nos. 3,408,194 and 3,4,
No. 47,928, No. 3,933,501 and No. 4,022,620, etc., oxygen atom elimination type yellow couplers or Japanese Patent Publication No. 58-10739, U.S. Pat. No. 4,401,752.
No. 4,326,024, RD18053 (April 1979)
Mon), British Patent No. 1,425,020, West German Published Application No. 2,219,9
No. 17, No. 2,261,361, No. 2,329,587 and No. 2,
A typical example thereof is a nitrogen atom-releasing yellow coupler described in JP-A No. 433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat.
1,082, 2,343,703, 2,600,788, 2,9
No. 08,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,
Nitrogen atom leaving groups described in 619 or U.S. Pat.
The arylthio groups described in 51,897 are particularly preferred.
Further, it has a ballast group described in European Patent No. 73,636. 5
-Pyrazolone couplers provide high color density. As the pyrazoloazole coupler, U.S. Pat.
432 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] described in US Pat. No. 3,725,067
[1,2,4] Triazoles, Research Disclosure No. 24220 (June 1984) and JP-A-60
-35552 and Research Disclosure, No. 24230 (19)
June 1984) and the pyrazolopyrazoles described in JP-A-60-43659. U.S. Pat. No. 4,50 in terms of low yellow sub-absorption of a coloring dye and light fastness
The imidazo [1,2-b] pyrazoles described in 0,630 are preferred, and the pyrazolo [1,5-b] [1, described in EP119,860A.
2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4 , 1
Representative examples thereof include oxygen atom elimination type two-equivalent naphthol couplers described in Nos. 46,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,826 and the like.

Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta 1-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,722,162 and 3,758,308,
No. 4,126,396, No. 4,334,011, No. 4,327,173
, German Patent Publication No. 3,329,729 and European Patent No. 121,3
2,5-diacylamino-substituted phenol couplers described in U.S. Pat. No. 65 and U.S. Pat.Nos. 3,446,622 and 4,3.
33,999, 4,451,559 and 4,427,7
No. 67, etc., and a phenolic coupler having a phenylureido group at the 2-position and an acylamino group at the 5-position.

In order to correct the unnecessary absorption of the chromophores, it is preferable to mask the color negative photosensitive material for photographing with a colored coupler. Yellow colored magenta couplers described in U.S. Pat. No. 4,163,670 and JP-B-57-39413, or U.S. Pat. Nos. 4,004,929 and 4,138,2.
Typical examples are magenta colored cyan couplers described in JP-A-58 and British Patent 1,146,368.
Other colored couplers are described in Research Disclosure, No. 17643, Item VII-G.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Specific examples of magenta couplers are described in U.S. Pat. No. 4,366,237 and British Patent 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing a development inhibitor, the couplers of the patents described in the above-mentioned Research Disclosure, No. 17643, VII to F are useful.

A preferred combination with the present invention is JP-A-57-
No. 151944, deactivating developer type; US Pat.
The timing type represented by 4,248,962 and JP-A-57-154234; the reaction type represented by JP-A-59-39653, and particularly preferred is JP-A-57.
-151944, 58-217932, Japanese Patent Application No. 5
9-75474, 59-82214, 59-8
No. 2214 and No. 59-90438, and developer deactivating DIR couplers and Japanese Patent Application No. 59-396.
53 is a reactive DIR coupler.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, for example, a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method, etc. are typical examples. be able to. In the oil-in-water dispersion method, after dissolving in either a single liquid of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are U.S. Pat.
It is described in No. 7, etc. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water, ultrafiltration or the like before being used for coating.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The light-sensitive material produced by using the present invention, as a color antifoggant or color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Take as an example. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. These layer arrangements can be arbitrarily selected as needed. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or blue-sensitive, red-sensitive and green-sensitive from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film, paper or cloth usually used for a photographic light-sensitive material or a rigid support such as glass, pottery or metal. To be done. Useful as flexible supports are cellulose derivatives (cellulose nitrate,
Films composed of cellulose acetate, cellulose acetate butyrate, etc.), synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (eg polyethylene, polypropylene, ethylene / butene copolymer). It is a paper or the like coated or laminated with the above. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, dip coating method, roller coating method, curtain coating method,
Various known coating methods such as extrusion coating method can be used. US Pat. No. 2,681,294 as required
No. 2761791, No. 3526528, No. 3508947, and the like, the multilayers may be simultaneously coated by the coating method.

The color photographic light-sensitive material according to the present invention is processed by the usual method described in Research Disclosure, No. 17643, pages 28 to 29 and No. 18716, page 651, left column to right column. be able to.
The first developer for reversal development is a black-and-white developer containing a silver halide solvent, and in order to perform sensitization processing using such a first developer, it is usually necessary to extend the time up to about 3 times that of the standard processing. Just go. At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened. The color photographic light-sensitive material of the present invention is usually subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. A typical example of the stabilizing treatment is a multistage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step. 2-9 in the case of this step
A countercurrent bath in the bath is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia mono) for adjusting the membrane pH (eg pH 3 to 8). Representative examples thereof include carboxylic acid, dicarboxylic acid, polycarboxylic acid and the like) and formalin. In addition, water softener (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinones, irithiazolones, 4-thiazoline) as required. Various additives such as benzimidazoles, halogenated phenols, etc.), surfactants, optical brighteners and hardeners may be used, or two or more of the same or different target compounds may be used in combination. Good.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

The present invention can be applied to various color light-sensitive materials. Representative examples include color reversal films for slides or televisions, and color reversal papers. The present invention can also be applied to a black-and-white light-sensitive material utilizing a three-color coupler mixture described in Research Disclosure No. 17123 (July 1978).

Example 1 A total of 10 types of silver iodobromide emulsions (iodine content: 3 mol%) as shown in Table 1 were prepared and used to prepare working and comparative samples of the present invention.

The detailed preparation method of these emulsions is described below.

Preparation of emulsion consisting of tabular grains; silver nitrate aqueous solution and KBr and K in a KI-free gelatin aqueous solution kept at 60 ° C. in an atmosphere of pBr1.3.
An aqueous solution containing I is added to silver nitrate in 10 minutes so that the number of moles of the halide is equal, and an emulsion comprising tabular grains having an average aspect ratio of 7.0 at 50% or more of the total grain projected area is formed. It was adjusted. The adjusted silver iodobromide grains have an average diameter in terms of spheres of 0.7 μ and an AgI of 3
It contained mol%. This core emulsion was then divided into two equal parts and shells were formed under the following separate conditions.

Emulsion A: The same silver nitrate and halogen solution as in the first core formation were used to precipitate a shell having a number of moles corresponding to 50% of the silver halide amount of the core at 60 ° C. for 3 minutes. Further, 2 mg of sodium thiosulfate and 2.5 mg of potassium chloroaurate were added to 1 mol of silver, and the mixture was heated at 70 ° C. for 30 minutes for chemical sensitization.

Emulsion B: The above core was chemically sensitized under the same conditions as Emulsion A, and then the shell was precipitated under the same conditions as Emulsion A.

Emulsion C: When the core of Emulsion A was formed, the temperature in the reaction solution was adjusted to 50
The temperature was maintained at 0 ° C. to form 0.4 μ core particles, and the subsequent steps were similar to those for Emulsion A.

Emulsion D: A core similar to Emulsion C was formed, and the subsequent steps were similar to those of Emulsion B.

Preparation of emulsion consisting of thick plate-like grains having an average aspect ratio of 3.0; silver nitrate aqueous solution and KBr and K in a KI-free gelatin aqueous solution kept at 65 ° C. in an atmosphere of pBr 0.8.
An aqueous solution containing I was added to silver nitrate in 5 minutes so that the number of moles of the above halide was equal, and physically ripened for 30 minutes to prepare an emulsion composed of thick plate-like grains with an average aspect ratio of 3.0. did. The prepared silver iodobromide grains have an average diameter in terms of spheres of 0.7 μm, and AgI
Was contained in an amount of 3 mol%. Next, this core emulsion was equally divided into two parts, and emulsion E was prepared through steps corresponding to emulsion A for the shell formation and chemical sensitization steps.

Emulsion G: The temperature in the reaction vessel during the core formation of Emulsion E was set to 5
By keeping at 5 ° C., 0.4 μ core particles were formed, and the subsequent steps were prepared in the same manner as in Emulsion A.

Emulsion H: A core similar to Emulsion G was formed, and the subsequent steps were similar to those of Emulsion B.

Preparation of a monodisperse emulsion having a (111) crystal habit; an aqueous silver nitrate solution and an aqueous solution containing KBr and KI were added by a double jet for 30 minutes while keeping pBr at 3.3 in an aqueous gelatin solution kept at 70 ° C. A monodisperse emulsion having a (111) crystal habit was prepared.

The emulsion grains had an average diameter of 0.7 μm in terms of sphere and contained 3 mol% of AgI. Next, this core emulsion is equally divided into two parts, and the shell formation and the chemical sensitization step are carried out through the steps corresponding to the emulsion A and the emulsion I respectively.
Was prepared.

Emulsion K: The temperature in the reaction vessel during the core formation of Emulsion I was 55
It was prepared by forming a core particle of 0.4 μm by keeping at 0 ° C., and then forming the shell in the same manner as Emulsion A by keeping pBr at 3.3.

Emulsion L: A core similar to Emulsion K was formed, and the subsequent steps were similar to those of Emulsion B, except that pBr was kept at 3.3 to form a shell.

Preparation of monodisperse emulsion having (100) crystal habit; Only crystal habit corresponding to I, K and L was prepared by the same method except that pBr at the time of grain formation of emulsions I, K and L was changed to 4.5. Different cubic monodisperse emulsions were prepared,
Emulsions M, O, and P were used.

On a subbed cellulose triacetate film support,
Multi-layer color light-sensitive materials each having the following composition were prepared and used as samples 101 to 108.

First layer: antihalation layer Black colloidal silver 0.25 g / m ² UV absorber U-1 0.04 g / m ² UV absorber U-2 0.1 g / m ² UV absorber U-3 0.1 g / ^{m 2} high-boiling organic solvent O-1 0.1 gelatin layer containing cc / ^{m 2} (dry thickness 2.mu.) second layer: intermediate layer compound H-1 0.05g / ^{m 2} high-boiling organic solvent O- 2 Gelatin layer containing 0.05 cc / m ² (dry film thickness 1 μ) Third layer: first red-sensitive emulsion layer Silver bromide emulsion G spectrally sensitized with sensitizing dyes S-1 and S-2 Silver amount · · 0.5 g / ^{m 2} coupler C-1 0.2 g / ^{m 2} coupler C-2 0.05 g / ^{m 2} high-boiling organic solvent O-2 0.12 cc / ^m gelatin layer containing ² (dry film Thickness 1 μ) Fourth layer: second red-sensitive emulsion layer Silver bromide emulsion E spectrally sensitized with sensitizing dyes S-1 and S-2 Silver amount ... 0.8 / ^{M 2} Coupler C-1 0.55 g / ^{m 2} Coupler C-2 0.14 g / ^{m 2} gelatin layer containing a high-boiling organic solvent ^O-2 0.33cc / ^m 2 (dry film thickness 2.5 [mu]) 5 Layer: intermediate layer Gelatin layer containing compound H-1 0.1 g / m ² high boiling point organic solvent O-2 0.1 cc / m ² (dry film thickness 1 μ) 6th layer: 1st green emulsion layer Silver iodobromide emulsion G containing dyes S-3 and S-4 Silver amount ... 0.7 g / m ² coupler C-3 0.35 g / m ² high boiling organic solvent O-2 0.26 cc / Gelatin layer containing m ² (dry film thickness 1 μm) Seventh layer: second green-sensitive emulsion layer Silver iodobromide emulsion E containing sensitizing dyes S-3 and S-4 Silver amount ... 0.7 g / m ² coupler C-4 0.25 g / ^{m 2} high-boiling organic solvent O-2 0.05 cc / ^m gelatin layer containing ² (dry film thickness 2.5 [mu]) eighth layer: intermediate Compound H-1 0.05g / ^{m 2} High-boiling organic solvent O-2 gelatin layer containing 0.1 g / ^{m 2} (dry film thickness 1 [mu]) Ninth layer: Yellow filter layer Yellow colloidal silver 0.1 g / m ² compound H-1 0.02 g / m ² compound H-2 0.03 g / m ² gelatin layer containing high boiling point organic solvent O-2 0.04 cc / m ² (dry film thickness 1 μm) 10th layer: 1st Blue-sensitive emulsion layer (described in Table 2) Silver iodobromide emulsion containing sensitizing dye S-5 Silver amount ... 0.6 g / m ² coupler C-5 0.5 g / m ² high boiling organic Gelatin layer containing solvent O-2 0.1 cc / m ² (dry film thickness: 1.5 μm) Eleventh layer: second blue-sensitive emulsion layer (described in Table 2) Iodine containing sensitizing dye S-5 gelatin containing silver bromide emulsion silver ·· 1.1 g / ^{m 2} coupler C-5 1.2 g / ^{m 2} high-boiling organic solvent ^O-2 0.23cc / ^m 2 Layer (dry film thickness 3.mu.) 12th layer: 1st protective layer UV absorber U-1 0.02g / ^{m 2} UV absorber ^U-2 0.03g / ^m 2 UV absorber U-3 0.03g / m ² UV absorber U-4 0.29 g / m ² High boiling point organic solvent O-1 Gelatin layer containing 0.28 cc / m ² (dry film thickness 2 μm) 13th layer: 2nd protective layer Fine particles whose surface is fogged Silver iodobromide emulsion Silver amount 0.1 g / m ² (iodine content 1 mol%, average particle size 0.06 μ) Gelatin layer containing polymethylmethacrylate particles (average particle size 1.5 μ) (dry film thickness) 0.8 μ) In addition to the above composition, gelatin hardener H-3 and a surfactant were added to each layer.

The compounds used to make the samples are shown below.

C-1 C-2 C-3 C-4 C-5 U-1 U-2 U-3 U-4 H-1 H-2 H-3 O-1 0-2 S-1 S-2 S-3 S-4 S-5 Each of the samples 101 to 108 thus obtained was exposed to a white wedge and subjected to the following development processing.

Processing time Process temperature Temperature 1st development 6 minutes 38 ° C Water wash 2 minutes 〃 Inversion 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Soaking 4 minutes 〃 Water washing 4 minutes 〃 Safety The composition of the 1-minute normal-temperature drying treatment liquid is as follows.

First developer water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt
2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-Phenyl-4methyl-4-hydroxymethyl-3pyrazolidone
2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added 1000 ml Inversion solution water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt
3 g stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water added 1000 ml color developer water 700 ml nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt
3 g sodium sulfite 7 g tribasic sodium phosphate (12-hydrate) 36 g potassium bromide 1 g potassium iodide (0.1% solution) 90 ml sodium hydroxide 3 g citrazinate 1.5 g N-ethyl-N- (β-methanesulfone Amidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 3,6-dithiaoctane-1,8-diol 1 g Water was added to 1000 ml Preparation liquid water 700 ml Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water added 1000 ml Bleached water 800 ml Sodium ethylenediaminetetraacetate (dihydrate) 2 g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) 120 g Potassium bromide 100 g Water added 1000 ml Fixer water 800 ml sodium thiosulfate Added 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Water 1000ml stabilizing solution water 800ml Formalin (37 wt%) 5.0 ml Fuji drywell (Fuji Film Co., Ltd. Surfactant)
The color reversal sensitivity of 1000 ml with the addition of 5.0 ml water was compared based on the relative exposure amount from the minimum density to 0.2. The sharpness is measured by MTF-
Displayed by value.

MTF-values are described in James, Theory of Photographic Processes, Fourth Edition (1977) P596 and P604.

As is clear from Table 1, according to the present invention, it is possible to simultaneously improve the sensitivity of the blue-sensitive layer and the sharpness of all the color-sensitive layers.

Example 2 Samples 109 to 113 were prepared by changing the emulsion of the green-sensitive emulsion layer of Sample 101 as shown in Table 3, and the photographic performances were compared.

As is clear from Table 2, according to the present invention, the sensitivity of the green-sensitive layer and the sharpness of the green-sensitive layer and the red-sensitive layer can be simultaneously achieved.

Example 3 Samples 115 to 128 were prepared by changing the emulsion of the blue-sensitive emulsion layer of Sample 101 as shown in Table 4,
The photographic performance was compared.

As is clear from Table 3, an emulsion in which the inside of the grain is chemically sensitized is used as the first blue-sensitive emulsion, and tabular grains which form a latent image on the surface or inside of the second blue-sensitive emulsion are formed. By using, it is possible to simultaneously improve the sensitivity of the blue-sensitive layer and the sharpness of the entire color-sensitive layer.

Example 4 Samples 129 to 133 were prepared by changing the emulsion of the green-sensitive emulsion layer of Sample 101 as shown in Table 4, and the photographic performances were compared.

As is apparent from Table 4, when the emulsion in which the inside of the grain is chemically sensitized is used for the first green-sensitive emulsion and the tabular grains are used for the second green-sensitive emulsion, the sensitivity of the green-sensitive layer and the green-sensitive layer are improved. The sharpness of the red-sensitive layer can be improved at the same time.

(Preferred Embodiment) 1. The silver halide color reversal photographic material according to the claims, which is coated with a negative type silver halide emulsion layer.

2. A silver halide color reversal photographic material according to claim 1, which has at least two layers of blue-sensitive, green-sensitive and red-sensitive emulsion layers having different sensitivities.

3. The silver halide color reversal photographic material according to claim 1, wherein the silver halide grains chemically sensitized inside the grains are tabular, octahedral, cubic, spherical or tetradecahedral grains.

4. The silver halide color reversal photographic material according to the claims, wherein the tabular halide grains are internal latent type.

5. The tabular silver halide grains and the silver halide grains chemically sensitized inside the grains are silver iodobromide, silver bromide, silver chloroiodobromide, or a mixture thereof. Silver color reversal photographic material.

6. A silver halide color reversal photograph according to claim 1, wherein the tabular silver halide grains have a spherical equivalent diameter of about 0.5 to about 3.0 µ and a thickness of 0.3 µ or less and 0.05 µ or more. material.

7. The molar ratio of silver ion in the core to the shell is 1: 1 to 1
A silver halide color reversal photographic material according to claim 1 containing silver halide grains chemically sensitized inside the grain, such as 9: 1.

(Effects of the Invention) The present invention provides high sensitivity and / or high sensitivity when a blue-sensitive, green-sensitive or red-sensitive silver halide emulsion layer of a multilayer silver halide color reversal photographic material is composed of a plurality of emulsion layers having different sensitivities. Alternatively, tabular grains are used for the medium-speed layer to eliminate the disadvantages caused by improving the sharpness of the lower layer based on the optical characteristics. In particular, the tabular grains have high dissolution physical development activity in the first development in the reverse color processing.
This is thought to be due to the fact that the silver halide is thin and has a large surface area, but the surface sensitization by excessively promoting the dissolution of the small size silver halide photosensitive grains contained in the adjacent emulsion layers, especially on the low sensitivity side. This results in a loss of sensitivity of the mold particles. By combining the silver halide grains chemically sensitized in the grain according to the present invention, it is possible to cause the photosensitive grain to be originally developed, and it is possible to obtain the tone reproduction and tone balance intended for the reversal color image. It can be achieved and imparts the desired image quality and processing stability to color reversal photographic materials that require particularly delicate final quality.

Claims (1)

[Claims] 1. A tabular silver halide in which at least 50% of the total projected area of silver halide grains contained in one silver halide emulsion layer coated on a support has an average aspect ratio of 5 or more. The silver halide emulsion layer occupied by the grains and having substantially the same color sensitivity as this silver halide emulsion layer but having a low photosensitivity contains silver halide grains chemically sensitized inside the grains. A silver halide color reversal photographic material which is subjected to color processing after black and white development.